CN108103341B - A kind of fabricated in situ ZrN enhancing Cu-base composites and its preparation method and application - Google Patents

A kind of fabricated in situ ZrN enhancing Cu-base composites and its preparation method and application Download PDF

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CN108103341B
CN108103341B CN201711396352.3A CN201711396352A CN108103341B CN 108103341 B CN108103341 B CN 108103341B CN 201711396352 A CN201711396352 A CN 201711396352A CN 108103341 B CN108103341 B CN 108103341B
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zrn
base composites
fabricated
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ball
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CN108103341A (en
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罗平
董仕节
汤臣
张艳华
蓝彬栩
陈晨
王义金
胡东伟
夏露
肖瑶
李智
覃富城
王冲
杨祺
邓宇鑫
张海一
晁飞扬
王书文
徐小涵
张佳琪
陈岗
方泽成
邵轩宇
夏宇欣
左雨菲
丁文祥
易少杰
陈成
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Hubei University of Technology
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making alloys
    • C22C1/04Making alloys by powder metallurgy
    • C22C1/05Mixtures of metal powder with non-metallic powder
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/02Compacting only
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10Sintering only
    • B22F3/1003Use of special medium during sintering, e.g. sintering aid
    • B22F3/1007Atmosphere
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/17Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by forging
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K11/00Resistance welding; Severing by resistance heating
    • B23K11/30Features relating to electrodes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C32/00Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides whether added as such or formed in situ
    • C22C32/0047Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
    • C22C32/0068Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only nitrides
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C9/00Alloys based on copper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/17Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by forging
    • B22F2003/175Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by forging by hot forging, below sintering temperature
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER
    • B22F2998/00Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10Processes characterised by the sequence of their steps
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER
    • B22F2999/00Aspects linked to processes or compositions used in powder metallurgy

Abstract

The present invention provides a kind of preparation methods of fabricated in situ ZrN enhancing Cu-base composites, first zirconium powder are carried out ball milling in a nitrogen atmosphere, obtain ZrN presoma;Then ZrN presoma and pure copper powder are subjected to wet ball grinding, obtain mixture;Obtained mixture is successively dried, the processing of cold moudling, sintering and forging and stamping, obtains fabricated in situ ZrN enhancing Cu-base composites.The fabricated in situ ZrN obtained the present invention also provides above-mentioned preparation method enhances Cu-base composites.Application the present invention also provides fabricated in situ ZrN prepared by the preparation method enhancing Cu-base composites as spot-wedling electrode material.Method provided by the invention effectively increases the hardness and wear-resisting property of ZrN enhancing Cu-base composites.Embodiment the result shows that, the hardness for the ZrN Cu-base composites that the method for the invention is prepared is above 180HV, and electrode life is up to 2650 points.

Description

A kind of fabricated in situ ZrN enhancing Cu-base composites and its preparation method and application
Technical field
The invention belongs to metal-base composites technical fields, relate generally to fabricated in situ ZrN enhancing Cu-base composites And its preparation method and application.
Background technique
Resistance spot welding is the major way of current vehicle body production.According to statistics, any cost of spot welding is 5 cents, production one Car will weld at 3000 points, and cost is 150 dollars, and the 1/2-3/4 of cost comes from the using and be lost of spot-wedling electrode.In sedan-chair A car needs to weld 7000-12000 point on vehicle body assembling line.In pinpoint welding procedure, spot-wedling electrode will bear machinery repeatedly The effect of power and heat, is inevitably plastically deformed.And electrode hardness is low and wears no resistance that will lead to plastic deformation serious, The direct result of electrode plastic deformation will lead to current density in welding process and reduce, and then make the joule generated in welding process Heat is reduced, and finally influences quality of welding spot.It can be seen that if some effective measures can be taken to improve the hardness of electrodes and wear-resisting Performance, it will weaken the plastic deformability of electrode, to extend the service life of electrode.
Currently, common electrode material there are Cu-base composites, mostly enhanced using the method for dispersion-strengtherning copper-based compound The hardness and wearability of material.Dispersion-strengtherning is one kind by being directly added into reinforced phase in basis material, to improve compound The method of material hardness.In the prior art, the hardness and wearability of the Cu-base composites obtained by dispersion-strengtherning still compared with It is low, Cu-base composites are limit in the application in spot-wedling electrode field.
Summary of the invention
In order to improve the hardness and wearability of Cu-base composites, the present invention provides a kind of fabricated in situ ZrN to enhance copper Based composites and preparation method thereof.
The present invention provides a kind of preparation methods of fabricated in situ ZrN enhancing Cu-base composites, include the following steps:
(1) zirconium powder is subjected to ball milling in a nitrogen atmosphere, obtains ZrN presoma;
(2) the ZrN presoma and pure copper powder obtained the step (1) carries out wet ball grinding, obtains mixture;
(3) mixture that the step (2) obtains successively is dried, the processing of cold moudling, sintering and forging and stamping, is obtained Fabricated in situ ZrN enhances Cu-base composites.
Preferably, the revolving speed of ball milling is 300~500 revs/min in the step (1), the ratio of grinding media to material of the ball milling is 10~ 30:1, the ball milling carry out under an inert atmosphere.
Preferably, ZrN presoma and the mass ratio of pure copper powder are 0.5~2:48~50 in the step (2).
Preferably, the drying in the step (3) is vacuum drying, and the temperature of the drying is 80~100 DEG C, dry Pressure be 0.01~0.1MPa, the dry time be 12~for 24 hours.
Preferably, the temperature of cold moudling is 20~30 DEG C in the step (3).
Preferably, the pressing mode of cold moudling is bidirectional pressing, the gross pressure of the bidirectional pressing in the step (3) For 300~500MPa;The dwell time of the cold moudling is 1~3min.
Preferably, sintering carries out under an inert atmosphere in the step (3), and the temperature of the sintering is 900~1050 DEG C; The time of the sintering is 10~30min.
Preferably, the temperature of forging and stamping processing is 500~550 DEG C in the step (3), and the forging and stamping number of processing is 5 ~10 times;The single deformation quantity of the forging and stamping processing is independently below 30%.
The present invention also provides fabricated in situ ZrN prepared by the preparation method to enhance Cu-base composites, packet The ZrN reinforced phase of Copper substrate and fabricated in situ is included, the ZrN Dispersion of Reinforcement is in the inside and surface of Copper substrate.
The present invention also provides fabricated in situ ZrN prepared by the preparation method to enhance Cu-base composites conduct The application of spot-wedling electrode material.
The present invention provides a kind of preparation methods of fabricated in situ ZrN enhancing Cu-base composites, first by zirconium powder in nitrogen Ball milling is carried out under gas atmosphere, obtains ZrN presoma;Then ZrN presoma and pure copper powder are subjected to wet ball grinding, are mixed Object;Obtained mixture is successively dried, the processing of cold moudling, sintering and forging and stamping, it is copper-based to obtain fabricated in situ ZrN enhancing Composite material.Method provided by the invention is by using ZrN as reinforced phase, by the method for dispersion-strengtherning by ZrN Dispersion of Reinforcement Inside Copper substrate and surface, the hardness and wearability of Cu-base composites are improved;And the present invention passes through first fabricated in situ ZrN presoma, then ZrN enhancing Cu-base composites are synthesized, the generation of impurity phase Zr-Cu, Cu-N is avoided, is further improved The hardness and wearability of ZrN Cu-base composites.Embodiment the result shows that, the ZrN copper that the method for the invention is prepared The hardness of based composites is above 180HV, and electrode life is up to 2650 points.
Detailed description of the invention
Fig. 1 is the metallograph for the copper product that comparative example 1 of the present invention is prepared;
Fig. 2 is the structural schematic diagram of spot-wedling electrode prepared by comparative example 1~2 of the present invention and Examples 1 to 5;
Fig. 3 is the metallograph for the Cu-base composites that comparative example 2 of the present invention is prepared;
Fig. 4 is the metallograph for the Cu-base composites that the embodiment of the present invention 1 is prepared;
Fig. 5 is the metallograph for the Cu-base composites that the embodiment of the present invention 2 is prepared;
Fig. 6 is the metallograph for the Cu-base composites that the embodiment of the present invention 3 is prepared;
Fig. 7 is the metallograph for the Cu-base composites that the embodiment of the present invention 4 is prepared;
Fig. 8 is the metallograph for the Cu-base composites that the embodiment of the present invention 5 is prepared;
Fig. 9 is the electrode life statistical chart of spot-wedling electrode prepared by comparative example 1~2 of the present invention and Examples 1 to 5.
Specific embodiment
The present invention provides a kind of preparation methods of fabricated in situ ZrN enhancing Cu-base composites, include the following steps:
(1) zirconium powder is subjected to ball milling in a nitrogen atmosphere, obtains ZrN presoma;
(2) the ZrN presoma and pure copper powder obtained the step (1) carries out wet ball grinding, obtains mixture;
(3) mixture that the step (2) obtains successively is dried, the processing of cold moudling, sintering and forging and stamping, is obtained Fabricated in situ ZrN enhances Cu-base composites.
Zirconium powder is carried out ball milling by the present invention in a nitrogen atmosphere, obtains ZrN presoma.In the present invention, the zirconium powder Partial size is preferably 100~200 mesh, further preferably 120~170 mesh, more preferably 140~170 mesh;The purity of the nitrogen It is preferred that >=99.9%.In the present invention, the molar ratio of the zirconium powder and nitrogen is preferably 2:1.Zirconium powder of the present invention is in nitrogen Mechanical ball mill is carried out under atmosphere and generates ZrN presoma.
In the present invention, the ZrN presoma is mainly some metastable phase titanium carbon compounds being made of Zr, N element, by In its unstable physical property, the nitrogen zirconium compounds of metastable phase is allowed to undergo phase transition acquisition in the subsequent sintering process ZrN reinforced phase, this enhances Cu-base composites for fabricated in situ ZrN and provides possibility.
In the present invention, the ball milling carries out under an argon atmosphere;The revolving speed of the ball milling is preferably 300~500 turns/ Point, further preferably 350~450 revs/min, more preferably 380~420 revs/min.In the present invention, the time of the ball milling Preferably 12~for 24 hours, further preferably 15~22h, more preferably 17~20h.In the present invention, the ratio of grinding media to material of the ball milling Preferably 10~30:1, further preferably 15~25:1, more preferably 18~22:1.In the present invention, the ball milling mill Ball and spherical tank material are preferably aluminium oxide, and the diameter of the abrading-ball is preferably 2~8mm, further preferably 5mm.The present invention makes With the abrading-ball and spherical tank material of oxidation aluminium material, the generation of by-product in mechanical milling process is avoided.
After obtaining ZrN presoma, the obtained ZrN presoma and pure copper powder are carried out wet ball grinding by the present invention, are obtained Mixture.
In the present invention, the partial size of the pure copper powder is preferably 100~200 mesh, further preferably 120~170 mesh, more Preferably 140~170 mesh;Purity >=99.9% of the pure copper powder.In the present invention, the ZrN presoma and pure copper powder Mass ratio is preferably (0.5~2): (48~50), further preferably (1~2): (48.5~50), more preferably (1.5~2): (49~50).
In the present invention, the revolving speed of the wet ball grinding is preferably 100~200 revs/min, further preferably 120~180 Rev/min, more preferably 150~180 revs/min;The time of the wet ball grinding is preferably 5~10h, further preferably 6~9h, More preferably 7~8h;The ratio of grinding media to material of the wet ball grinding is preferably 1~10:1, further preferably 3~8:1, and more preferably 5 ~6:1;The abrading-ball and spherical tank material of the wet ball grinding are preferably aluminium oxide, and the ball radius is preferably 2~8mm, into one Step is preferably 5mm.The present invention avoids the production of by-product in mechanical milling process using the abrading-ball and spherical tank material of oxidation aluminium material It is raw.In the present invention, the medium of the wet ball grinding is preferably dehydrated alcohol;The dosage of the dehydrated alcohol is preferably complete with energy Infiltration does not have subject to powder and abrading-ball.
The present invention uses wet ball grinding, realizes the uniform mixing of ZrN presoma and pure copper powder, obtains including ZrN presoma With the mixture of pure copper powder, the reunion between abrasive material is avoided, and wet ball grinding is conducive to separate between abrasive material and abrading-ball, nothing Pollution.
The present invention, which passes through, is first prepared in situ ZrN presoma, then mixes with copper powder, and the TiC enhancing for obtaining fabricated in situ is copper-based Composite material avoids zirconium powder, nitrogen and copper powder together ball milling generating asking for intermetallic compound Zr-Cu, Cu-N impurity phase Topic.
After obtaining mixture, the present invention obtained mixture is successively dried, at cold moudling, sintering and forging and stamping Reason obtains fabricated in situ ZrN enhancing Cu-base composites.
In the present invention, the drying is preferably dried in vacuo, and the pressure of the drying is preferably 0.01~0.1MPa, into One step is preferably 0.05~0.1MPa, more preferably 0.08~0.1MPa;The temperature of the drying is preferably 80~100 DEG C, into One step is preferably 85~95 DEG C, and more preferably 90~95 DEG C;The time of the drying is preferably 12~for 24 hours, further preferably 15~20h.The present invention eliminates the solvent on the mixture surface by being dried.
In the present invention, the preferably bidirectional pressure of the pressing mode of the cold moudling, the gross pressure of the bidirectional pressing Preferably 300~500MPa, further preferably 350~450MPa, more preferably 400~450MPa.In the present invention, described The temperature of cold moudling is preferably 20~30 DEG C, and further preferably 25~30 DEG C;The dwell time of the cold moudling is preferred For 1~3min, further preferably 2~3min.In the present invention, the green compact diameter of the cold moudling be preferably 35~ 45mm, further preferably 40mm.
The present invention is handled by cold moudling, so that fine and close consolidation between ZrN presoma and pure copper powder, and then improve most The consistency for the fabricated in situ ZrN enhancing Cu-base composites being prepared eventually.Fabricated in situ ZrN enhancing of the present invention is copper-based The relative density of composite material is up to 95% or more.
In the present invention, the sintering preferably carries out under an argon atmosphere, and the gas flow of the argon gas is preferably 1~ 3L/min, further preferably 2~3L/min.In the present invention, the temperature of the sintering is preferably 900~1050 DEG C, into one Preferably 950~1000 DEG C of step;The time of the sintering is preferably 10~30min, further preferably 15~25min, more excellent It is selected as 20~25min.
The present invention makes ZrN precursor in situ be changed into ZrN reinforced phase, while ZrN reinforced phase and copper powder by sintering processes During the sintering process, ZrN reinforced phase is evenly distributed on inside Copper substrate, is improved the performance of prepared Cu-base composites, is made Prepared Cu-base composites have higher hardness and wearability.
The present invention prepares ZrN reinforced phase by the method for fabricated in situ, and avoiding is caused using being directly added into ZrN reinforced phase Reinforced phase and matrix between binding force difference problem so that method provided by the invention be prepared ZrN enhancing copper Based composites hardness with higher and preferable wear-resisting property.
In the present invention, the temperature of the forging and stamping processing is preferably 500~550 DEG C, and further preferably 510~540 DEG C, More preferably 520~530 DEG C;The forging and stamping number of processing is preferably 5~10 times, and further preferably 6~8 times.The present invention In the forging and stamping treatment process, single deformation quantity is preferably 30% hereinafter, further preferably 10%~30%, more preferably 15%~25%.The present invention is handled by forging and stamping, improves the fabricated in situ ZrN enhancing Cu-base composites being finally prepared Hardness.
The present invention also provides the fabricated in situ ZrN that above-mentioned preparation method is prepared to enhance Cu-base composites, including The ZrN reinforced phase of Copper substrate and fabricated in situ, the ZrN Dispersion of Reinforcement is in the inside and surface of Copper substrate.
Fabricated in situ ZrN enhancing Cu-base composites provided by the invention can be used as spot-wedling electrode materials'use.This hair Successively spot welding electricity can be obtained after machining and cold extrusion is handled in the fabricated in situ ZrN enhancing Cu-base composites of bright offer The Cu-base composites of pole.
Below with reference to embodiment to fabricated in situ ZrN provided by the invention enhancing Cu-base composites and preparation method thereof into Row detailed description, but they cannot be interpreted as limiting the scope of the present invention.
Comparative example 1
It is the pure copper powder of 200 mesh by granularity, by bidirectional pressing, pressure maintaining 2 minutes under 350MPa pressure, green compact diameter is 40 millimeters, green compact draw ratio is 1:2.In the case where flow is 2L/min ar gas environment, green compact is sintered at 950 DEG C, when heat preservation Between 30min.Under the conditions of controlling single deformation quantity less than 10%, sintered green compact is carried out forging and pressing 10 times repeatedly at 550 DEG C, Final diameter direction deformation quantity is about 50%, and length direction deformation quantity is about 300%, obtains copper-based material, Copper base material after processing The diameter of material is about 20mm, and length is about 40mm, relative density 99.2%.
Metallographic structure observation is carried out to the copper product of preparation, as a result as shown in Figure 1.
By treated, material passes through machining and subsequent cold-extrusion technology, is processed into the point of shape and size shown in Fig. 2 Welding electrode.
Comparative example 2
The zirconium nitride (ZrN) that 0.5g granularity is 200 mesh is weighed, with 49.5g pure copper powder in 200 revs/min of rotational speed of ball-mill, ball milling Time 10h, ratio of grinding media to material 10:1 are mixed well under soaked in absolute ethyl alcohol environment, and abrading-ball and spherical tank material are aluminium oxide, and abrading-ball is straight Diameter is 5mm.By the powder after ball milling at 0.01MPa, 95 DEG C drying time 24 hours.By the powder after vacuum drying, lead to Bidirectional pressing is crossed, 3min is kept the temperature at 500MPa, green compact diameter is 40mm.In the case where flow is 3 liters/min of ar gas environments, 1050 DEG C green compact is sintered, soaking time 30 minutes.Under the conditions of controlling single deformation quantity less than 10%, to sintered green compact It carrying out forging and pressing 10 times repeatedly at 550 DEG C, the total deformation quantity in final diameter direction is about 50%, and length direction deformation quantity is about 300%, ZrN enhancing Cu-base composites are obtained, the diameter that ZrN enhances Cu-base composites after processing is about 20mm, and length is about 40mm, Relative density is 99.2%.
Metallographic structure observation is carried out to the ZrN enhancing Cu-base composites of preparation, as a result as shown in Figure 3.
By treated, material passes through machining and subsequent cold-extrusion technology, is processed into the point of shape and size shown in Fig. 2 Welding electrode.
Embodiment 1
The zirconium powder of 10g is weighed, carries out ball milling in a nitrogen atmosphere, zirconium powder granularity is 200 mesh, purity >=99.99, nitrogen Zirconium powder and nitrogen ball milling 12h are controlled 350 revs/min of revolving speed, ratio of grinding media to material 10:1, abrading-ball and the ball of ball milling by purity >=99.9% Tank material is aluminium oxide, ball radius 5mm.Mechanical milling process is completed under argon gas protection environment of the purity greater than 99.9%, is obtained To ZrN presoma.
It is in 120 revs/min of rotational speed of ball-mill, ratio of grinding media to material with pure copper powder that 49.5g granularity is 200 mesh by 0.5g ZrN presoma In 2:1 and anhydrous ethanol medium, mixture is obtained within ball milling 10 hours, and abrading-ball and spherical tank material are aluminium oxide, ball radius For 5mm.
By the mixture after ball milling at pressure 0.01MPa, 80 DEG C drying time 24 hours.It will be mixed after vacuum drying It closes object and, at 20 DEG C, keeps the temperature 3 minutes under 300MPa by bidirectional pressing, green compact diameter is 40mm.
Green compact after molding is sintered 30min under argon gas protection environment, controls 2 liters/min of argon gas flow, sintering temperature 900 DEG C, obtain green compact.
Under the conditions of controlling single deformation quantity less than 10%, sintered green compact is carried out forging and pressing 10 times repeatedly at 500 DEG C, Final diameter direction deformation quantity is about 50%, and length direction deformation quantity is about 300%, and it is copper-based multiple to obtain fabricated in situ ZrN enhancing Condensation material, the diameter that fabricated in situ ZrN enhances Cu-base composites after processing is about 20mm, and length is about 40mm, relative density It is 98.2%.
Metallographic structure observation is carried out to the fabricated in situ ZrN enhancing Cu-base composites of preparation, as a result as shown in Figure 4.
By treated, material passes through machining and subsequent cold-extrusion technology, is processed into the point of shape and size shown in Fig. 2 Welding electrode.
Embodiment 2
The zirconium powder of 10g is weighed, carries out ball milling in a nitrogen atmosphere, zirconium powder granularity is 200 mesh, purity >=99.99, nitrogen Zirconium powder and nitrogen ball milling 18h are controlled 400 revs/min of revolving speed, ratio of grinding media to material 20:1, abrading-ball and the ball of ball milling by purity >=99.9% Tank material is aluminium oxide, ball radius 5mm.Mechanical milling process is completed under argon gas protection environment of the purity greater than 99.9%, is obtained To ZrN presoma.
It is the pure copper powder of 200 mesh in 150 revs/min of rotational speed of ball-mill, ratio of grinding media to material 4:1 by 1g ZrN presoma and 49g granularity And in anhydrous ethanol medium, mixture is obtained within ball milling 8 hours, and abrading-ball and spherical tank material are aluminium oxide, ball radius is 5mm。
By the mixture after ball milling at pressure 0.03MPa, 85 DEG C drying time 20 hours.It will be mixed after vacuum drying It closes object and, at 20 DEG C, keeps the temperature 3 minutes under 400MPa by bidirectional pressing, green compact diameter is 40mm.
Green compact after molding is sintered 30min under argon gas protection environment, controls 3 liters/min of argon gas flow, sintering temperature 950 DEG C, obtain green compact.
Under the conditions of controlling single deformation quantity less than 20%, sintered green compact is carried out forging and pressing 10 times repeatedly at 500 DEG C, Final diameter direction deformation quantity is about 50%, and length direction deformation quantity is about 300%, and it is copper-based multiple to obtain fabricated in situ ZrN enhancing Condensation material, the diameter that fabricated in situ ZrN enhances Cu-base composites after processing is about 20mm, and length is about 40mm, relative density It is 98.6%.
Metallographic structure observation is carried out to the fabricated in situ ZrN enhancing Cu-base composites of preparation, as a result as shown in Figure 5.
By treated, material passes through machining and subsequent cold-extrusion technology, is processed into the point of shape and size shown in Fig. 2 Welding electrode.
Implementation column 3
The zirconium powder of 10g is weighed, carries out ball milling in a nitrogen atmosphere, zirconium powder granularity is 200 mesh, purity >=99.99, nitrogen Purity >=99.9% for 24 hours by zirconium powder and nitrogen ball milling controls 500 revs/min of revolving speed, ratio of grinding media to material 30:1, abrading-ball and the ball of ball milling Tank material is aluminium oxide, ball radius 5mm.Mechanical milling process is completed under argon gas protection environment of the purity greater than 99.9%, is obtained To ZrN presoma.
It is in 180 revs/min of rotational speed of ball-mill, ratio of grinding media to material with pure copper powder that 48.5g granularity is 200 mesh by 1.5g ZrN presoma In 6:1 and anhydrous ethanol medium, mixture is obtained within ball milling 6 hours, and abrading-ball and spherical tank material are aluminium oxide, ball radius is 5mm。
By the mixture after ball milling at pressure 0.05MPa, 90 DEG C drying time 18 hours.It will be mixed after vacuum drying It closes object and, at 30 DEG C, keeps the temperature 1 minute under 500MPa by bidirectional pressing, green compact diameter is 40mm.
Green compact after molding is sintered 20min under argon gas protection environment, controls 3 liters/min of argon gas flow, sintering temperature 1000 DEG C, obtain green compact.
Under the conditions of controlling single deformation quantity less than 30%, sintered green compact is carried out forging and pressing 5 times repeatedly at 550 DEG C, Final diameter direction deformation quantity is about 50%, and length direction deformation quantity is about 300%, and it is copper-based multiple to obtain fabricated in situ ZrN enhancing Condensation material, the diameter that fabricated in situ ZrN enhances Cu-base composites after processing is about 20mm, and length is about 40mm, relative density It is 99.6%.
Metallographic structure observation is carried out to the fabricated in situ ZrN enhancing Cu-base composites of preparation, as a result as shown in Figure 6.
By treated, material passes through machining and subsequent cold-extrusion technology, is processed into the point of shape and size shown in Fig. 2 Welding electrode.
Embodiment 4
The zirconium powder of 10g is weighed, carries out ball milling in a nitrogen atmosphere, zirconium powder granularity is 200 mesh, purity >=99.99, nitrogen Purity >=99.9% for 24 hours by zirconium powder and nitrogen ball milling controls 500 revs/min of revolving speed, ratio of grinding media to material 30:1, abrading-ball and the ball of ball milling Tank material is aluminium oxide, ball radius 5mm.Mechanical milling process is completed under argon gas protection environment of the purity greater than 99.9%, is obtained To ZrN presoma.
It is the pure copper powder of 200 mesh in 200 revs/min of rotational speed of ball-mill, ratio of grinding media to material 8:1 by 2g ZrN presoma and 48g granularity And in anhydrous ethanol medium, mixture is obtained within ball milling 5 hours, and abrading-ball and spherical tank material are aluminium oxide, ball radius is 5mm。
By the mixture after ball milling at pressure 0.08MPa, 95 DEG C drying time 16 hours.It will be mixed after vacuum drying It closes object and, at 30 DEG C, keeps the temperature 1 minute under 500MPa by bidirectional pressing, green compact diameter is 40mm.
Green compact after molding is sintered 30min under argon gas protection environment, controls 3 liters/min of argon gas flow, sintering temperature 1050 DEG C, obtain green compact.
Under the conditions of controlling single deformation quantity less than 10%, sintered green compact is carried out forging and pressing 10 times repeatedly at 550 DEG C, Final diameter direction deformation quantity is about 50%, and length direction deformation quantity is about 300%, and it is copper-based multiple to obtain fabricated in situ ZrN enhancing Condensation material, the diameter that fabricated in situ ZrN enhances Cu-base composites after processing is about 20mm, and length is about 40mm, relative density It is 98.9%.
Metallographic structure observation is carried out to the fabricated in situ ZrN enhancing Cu-base composites of preparation, as a result as shown in Figure 7.
By treated, material passes through machining and subsequent cold-extrusion technology, is processed into the point of shape and size shown in Fig. 2 Welding electrode.
Embodiment 5
The zirconium powder of 10g is weighed, carries out ball milling in a nitrogen atmosphere, zirconium powder granularity is 200 mesh, purity >=99.99, nitrogen Purity >=99.9% for 24 hours by zirconium powder and nitrogen ball milling controls 500 revs/min of revolving speed, ratio of grinding media to material 30:1, abrading-ball and the ball of ball milling Tank material is aluminium oxide, ball radius 5mm.Mechanical milling process is completed under argon gas protection environment of the purity greater than 99.9%, is obtained To ZrN presoma.
It is in 100 revs/min of rotational speed of ball-mill, ratio of grinding media to material with pure copper powder that 47.5g granularity is 200 mesh by 2.5g ZrN presoma In 10:1 and anhydrous ethanol medium, mixture is obtained within ball milling 8 hours, and abrading-ball and spherical tank material are aluminium oxide, ball radius For 5mm.
By the mixture after ball milling at pressure 0.1MPa, 100 DEG C drying time 12 hours.It will be mixed after vacuum drying It closes object and, at 20 DEG C, keeps the temperature 2 minutes under 500MPa by bidirectional pressing, green compact diameter is 40mm.
Green compact after molding is sintered 30min under argon gas protection environment, controls 3 liters/min of argon gas flow, sintering temperature 1050 DEG C, obtain green compact.
Under the conditions of controlling single deformation quantity less than 10%, sintered green compact is carried out forging and pressing 10 times repeatedly at 550 DEG C, Final diameter direction deformation quantity is about 50%, and length direction deformation quantity is about 300%, and it is copper-based multiple to obtain fabricated in situ ZrN enhancing Condensation material, the diameter that fabricated in situ ZrN enhances Cu-base composites after processing is about 20mm, and length is about 40mm, relative density It is 98.0%.
Metallographic structure observation is carried out to the fabricated in situ ZrN enhancing Cu-base composites of preparation, as a result as shown in Figure 8.
By treated, material passes through machining and subsequent cold-extrusion technology, is processed into the point of shape and size shown in Fig. 2 Welding electrode.
The spot-wedling electrode being processed into the Cu-base composites that comparative example 1~2 and Examples 1 to 5 are prepared is in phase With the life tests under welding parameter, as a result as shown in Figure 9.As shown in Figure 9, using point prepared by Cu-base composites of the present invention Welding electrode has longer service life.
The Cu-base composites that comparative example 1~2 and Examples 1 to 5 are prepared carry out hardness, relative density, electrode Service life and conductivity, the results are shown in Table 1;Wherein, the measurement standard of hardness is GB/T4340.1-2009;Relative density=reality Border density ÷ theoretical density × 100%;The measurement standard of electrode life is AWS-W-6858A;The measurement standard of conductivity is YS- T478-2005。
The performance comparison for the Cu-base composites that 1 comparative example 1~2 of table is prepared with Examples 1 to 5
According to 1 test result of table it is found that the preparation method of Cu-base composites provided by the invention can significantly improve copper The hardness of based composites.The electrode life of Cu-base composites provided by the present invention is it is found that provided by the invention copper-based multiple Condensation material wearability is preferable.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered It is considered as protection scope of the present invention.

Claims (10)

1. a kind of preparation method of fabricated in situ ZrN enhancing Cu-base composites, includes the following steps:
(1) zirconium powder is subjected to ball milling in a nitrogen atmosphere, obtains ZrN presoma;
(2) the ZrN presoma and pure copper powder obtained the step (1) carries out wet ball grinding, obtains mixture;
(3) mixture that the step (2) obtains successively is dried, cold moudling, sintering and forging and stamping processing, obtains original position Synthesizing ZrN enhances Cu-base composites.
2. preparation method according to claim 1, which is characterized in that in the step (1) revolving speed of ball milling be 300~ 500 revs/min, the ratio of grinding media to material of the ball milling is 10~30:1, and the ball milling carries out under an inert atmosphere.
3. preparation method according to claim 1, which is characterized in that ZrN presoma and pure copper powder in the step (2) Mass ratio is 0.5~2:48~50.
4. preparation method according to claim 1, which is characterized in that the drying in the step (3) is vacuum drying, institute State dry temperature be 80~100 DEG C, dry pressure be 0.01~0.1MPa, the dry time be 12~for 24 hours.
5. preparation method according to claim 1 or 4, which is characterized in that the temperature of cold moudling is in the step (3) 20~30 DEG C.
6. preparation method according to claim 5, which is characterized in that the pressing mode of cold moudling in the step (3) For bidirectional pressing, the gross pressure of the bidirectional pressing is 300~500MPa;The dwell time of the cold moudling is 1~3min.
7. preparation method according to claim 1, which is characterized in that in the step (3) sintering under an inert atmosphere into Row, the temperature of the sintering are 900~1050 DEG C;The time of the sintering is 10~30min.
8. preparation method according to claim 1, which is characterized in that the temperature of forging and stamping processing is 500 in the step (3) ~550 DEG C, the forging and stamping number of processing is 5~10 times;The single deformation quantity of the forging and stamping processing is independently below 30%.
9. the fabricated in situ ZrN enhancing Cu-base composites that any one of claim 1~8 preparation method is prepared, packet The ZrN reinforced phase of Copper substrate and fabricated in situ is included, the ZrN Dispersion of Reinforcement is in the inside and surface of Copper substrate.
10. fabricated in situ ZrN described in a kind of claim 9 enhances application of the Cu-base composites as spot-wedling electrode material.
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